Search Documents

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested' that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11'12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

By J. Chipman, J. A. Cordier

Equilibrium in the reaction H2 (g) + 2 = H2S (g) was studied at 1600°C for sulphur dissolved in Fe-Ni alloys of 0 to 100 pct Ni. Within experimental accuracy, the equilibrium ratio pH2s/pH2 [pct S] is independent of the Fe-Ni ratio. Its variation with sulphur content is the same in nickel and the alloys as in iron. Recent data on dissociation of S2 into atomic sulphur are used to apply a small correction to earlier equilibrium data. Equations are presented which define the thermodynamic properties of sulphur in liquid Fe-Ni alloys. ACTIVITY of sulphur in liquid iron was determined by Sherman, Elvander, and Chipman.' The effects of a number of alloying elements on the activity of sulphur also have been determined, that of silicon by Morris and Williams,2 that of carbon by Morris and Buehl,8 and the effects of manganese, phosphorus, and aluminum by Sherman and Chip-man.' The data of Rosenqvist and Cox5 have been used to establish the effect of copper. A summary of all of these data is included in the paper by Sherman and Chipman. In each case, the experimental method depended upon the study of equilibruim in the reaction of sulphur in the liquid metal with hydrogen gas to form H,S. Despite wide differences in the design of apparatus used by the several investigators, all of the results are in excellent agreement. Experimental Study Since the experimental method has already been described,' it will be sufficient to mention its general

Jan 1, 1956

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By Chester A. Rowland

INTRODUCTION Comminution is generally a feed preparation step for subsequent processing stages; exceptions being when a final product such as aggregates, specification sand, Portland Cement, and similar products is produced. Grinding, the fine product phase of comminution, requires a large capital investment and frequently is the area of maximum usage of power and wear resistant materials. Grinding is most frequently done in rotating drums utilizing loose grinding media, lifted by the rotation of the drum, to break the ores in various combinations of impact, attrition and abrasion to produce the specified product. Grinding media can be the ore itself (autogenous grinding -- primary and secondary), natural or manufactured non-metallic media (pebble milling) or manufactured metallic media -- steel rods, steel or iron balls. This chapter will discuss general mill design and the specific design and application of the following types of tumbling grinding mills. [Overflow Rod Mills Figure 1 Peripheral Discharge Rod Mills Figures 2 and 3 Compartment Mills Rod and Ball Figure 6 Ball Figure 6a Pebble Mill Figure 6b Overflow Ball Mills Figure 8 Diaphragm (Grate Discharge) Ball Mills Figure 9] I. GENERAL MILL DESIGN A. Liners The interior surface of grinding mills exposed to grinding media and/or the material being ground are protected from wear and corrosion by rubber, metallic, a combination of rubber and metallic, or non-metallic wear resistant materials. B. Drives Economics at the time of plant design and mill purchase determine the drive to be used. The simplest drive is the low speed synchronous motor with speeds in the range of 150 to 250 RPM connected to the mill pinion-shaft by either an air clutch or flexible coupling.

Jan 1, 1982

By W. E. Bonini, E. A. Hickok

IN the course of an investigation directed toward expanding ground-water facilities in Essex and Morris counties, New Jersey, the Board of Water Commissioners of the city of East Orange authorized a seismic-refraction survey' for the purpose of de-lineating bedrock topography below unconsolidated overburden. Results of the survey were highly satisfactory and led to the preparation of a comparatively detailed bedrock contour map. Knowledge of the bedrock depth and configuration was an important aid in selection of sites for test drilling. The portion of the East Orange Water Reserve under consideration is in the flood plain of the Pas-saic River about 10 miles west of Newark, N. J. The flood plain is about 175 ft above mean sea level and is bordered by low hills rising to elevations of approximately 250 ft. The bedrock underlying the Water Reserve consists of sandstone and shale of the Triassic Brunswick formation and is covered everywhere by deposits of unconsolidated glacial outwash sand and gravel, lacustrine clay, and recent river silt as much as 150 ft thick. Yield of wells in the sandstone and shale averages 100 to 200 gpm. Since production wells constructed in the sand and gravel aquifer in the buried river valley shown on the contour map (Fig. 1) yield 300 to 1400 gpm, it was proposed to locate additional production wells in this buried valley, where the yields per well would be maximum. In 1939 and 1946 the East Orange Water Dept. had electrical-resistivity surveys made to determine depths to bedrock. From the resistivity data the exploration company prepared a bedrock contour map. A well field expansion program begun in 1955 utilized this information to locate sites for test wells along a predicted northward extension of the buried valley in which existing production wells are located. After several test wells (wells 201-205) had been drilled, it became apparent that the resistivity information was unreliable." For example, test well 201 recorded bedrock at a depth of 72 ft, whereas the resistivity depth determination was 130 ft. As a consequence, the test drilling program was temporarily suspended and a seismic survey was under- taken to determine the topography and extent of the buried valley known from well records to underlie the existing well field. In the first phase of this study, several seismic shot point locations were placed at sites where well logs had been obtained previously. This procedure is necessary in a new area to determine whether the seismic method is applicable and what degree of accuracy is to be expected. At the East Orange Water Reserve, depths obtained from the shot points near test wells 202, 203, and 204 were within 8 to 11 pct of the depths logged (Table I). With this assurance that accurate results could be obtained, additional seismic spreads were located on the Water Reserve. Using a portable refraction seismograph, in the fall of 1955 a crew of four men shot a total of 29 reversed seismic spreads in a period equivalent to six field days. Charges as heavy as 3 1b of 40 pct dynamite were necessary at a few places to overcome ground vibrations caused by traffic on nearby highways. At most other sites, a 1-1b charge was sufficient. Travel-time plots were made for all spreads, and depths and true velocities were calculated according to formulas for multiple sloping layers by Ewing, Woollard, and Vine.' The plot of spread 7 (Fig. 2) is typical of the short spreads in which bedrock was shallow—about 50 ft in this case. Where there were not enough arrivals through the bedrock to define the high velocity bedrock line, the spreads were lengthened. This was done by placing shots on line several hundred feet away from each end of the line of geophones. It was then possible to construct complete reverse plots for both short and extended shot points (see spread 27, Fig. 3). Four individual depths were calculated from each extended spread. Three and in some cases four seismic layers were observed. The surficial layer had a velocity range of 900 to 1200 fps, the lowest velocity recorded. This seismic layer is above the water table and is interpreted as recent river silt. The bedrock had the highest velocities, which ranged from 10,600 to 16,400 fps. Intermediate velocities ranged from 4500 to 6800 fps. In every case the intermediate layer was within

Jan 1, 1959

By John H. Hall

The Frémont test for measuring the energy consumed in breaking a notched bar of steel is not so well known in this country as it deserves to be. The test specimen used in this test is about # by 6 by about 16 in., notched with a hack saw on the lower side to cause the piece to break at a fixed point. A weight of 10 kg. falling 4 m., and provided with a knife or chisel which strikes the specimen, breaks the test piece by impact. The residual force in the falling weight after it has broken the specimen is recorded by a suitable device, and the difference between the total energy and the residual energy of the weight (in kilogrammeters) is the force consumed in breaking the specimen. An experience of several years with the Frémont testing machine has shown its great value in readily detecting brittleness not revealed by tensile testing or slow bending testing. In this paper it is proposed to discuss (1) the supersensitiveness of the test as applied to cast steel and (2) its value in revealing the effect of heat treatment under certain conditions. In testing coupons cut from castings heat treated by quenching and annealing, attention was drawn to the wide variations in the value of the Frémont test of specimens cut from different parts of the coupon. The latter was of the form and dimensions shown in Fig. 1, and Fremont test pieces were cut from two parts of this coupon, marked A and B in that figure. The results of the tests are shown below, tests A and B in each instance being from the same coupon: A. B. A. B. Coupon. Kilogram- Kilogram- Coupon. Kilogram- Kilogram- meters. meters. meters. meters. 1,........ 12.0 12.5 9,........ 27.5 32.5 2,........ 11.0 32.5 10,........17.5 31.0 3,........ 11.5 30.0 11,........ 14.5 31.0 4,........ 20.0 33.0 12,........ 15.0 27.5 5,........ 17.5 33.0 13,........ 19.0 30.0 6,........ 17.5 20.0 14,........ 17.5 25.5 7,........ 17.5 13.0 15,........15.0 30.0 8,........ 10.0 30.0

Jan 1, 1914

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953

By C. E. Richards, C. N. Reid

The influence of preferred orientation on the incidence of defbrtnation tuinning has been studied. High-purity iron with almost vandonz grain orientation was cotnpared uitll iron of the sa)ne grain size and composilion lza,ing a strong (110) fiber texture. As expected from published work on single crgslfls, /he ))lean stress for the onset of luitzning-, and the l,olu)nt. fraclion of twinned nzaterial obserlled in lension differed fron the 1-a1ue.s it2 co?nPression for tnolerial with a slrong texlure. The llinning stress of "rctndorrl " )zalerial did not 17ary with the sense of the aPPlied unin.via1 stress, but sirprisinglg the incidence of 1c)i)zning- was about three 1i))zes greater ill conzp?&apos;ession Illon in lension. These results (Ire attributed entirely to ovienbation and may be nderslood in ler?ns of the shear slresses acting on the allowed twinning syster)is. J. HE twins most commonly formed in bcc metals may be described as regions of the crystal in which a particular set of (112) planes is homogeneously sheared by 0.707 in the appropriate ( 111) direction. A similar twin-related crystal could be produced by a shear of 1.414 in the reverse (111) direction but twinning by this large displacement has never been reported. Thus, twinning is unidirectional and a shear stress which produces twinning does not do so when its sense is reversed. The sense of a shear Stress is reversed when the loading is changed from tension to compression, or vice versa. Consequently, for a given orientation of a crystal relative to a uniaxial stress, only a fraction of the twelve (112) twinning systems are geometrically capable of operating in tension, and the remaining systems may operate only in compression. Therefore, when twinning is involved, there are expected to be differences in behavior between crystals tested in uniaxial tension and those tested in compression. This has been verified experimentally by Reid et 01.&apos; and Sherwood el al.,&apos; although a critical stress criterion was not encountered. Furthermore, twinning stresses in colmbium," tungten, tantalum,&apos; irn,&apos; i-Fe,\ nd molybdenum7 single crystals have been shown to depend critically on orientation, although again twinning did not occur at a critical value of the macroscopic shear stress. However, when twinning occurs, it generally does so on the most highly stressed systems, 1--4&apos;6&apos;8&apos;9 implying that the stress level does have some relevance to twin formation. In view of the large orientation dependence of twinning in bee single crystals, it might be expected that such an effect would be present in poly crystalline material which possesses a recrystallisation texture. Indeed, riestner" showed that the twinning stress in tension is very orientation-sensitive it1 <&apos;grain-oriented, silicon-iron;" this material possessed a very strong t c m^ii a nnr x_____k . i-_ii__ ri_______j. _x r»i_._:__i preferred orientation obtained by secondary recrystallisation. Reid et a/.&apos; observed a marked difference in the tensile and compressive yield stresses of polycrys-talline columbium which was rationalised in terms of the effect of a preferred orientation on twinning. No other such illformation is known to the authors. Several investigations of twinning in polycrystalline bcc metals have been reported in which the possible existence of a preferred orientation was not even mentioned. It is the purpose of this paper to show that there is a strong effect of texture on twinning in polycrystalline iron, and to poilt out the difficulty in eliminating preferred orientation in recrystallised metals. 1. EXPERIMENTAL METHOD Material and Specimen Preparation. Low-carbon, high-purity iron was obtained from the National Physical Laboratory in the form of $-in. diam rod which had been cold-swaged from a diam of 1 in. The composition of the material is given in Table I. The as-received bar was cold-swaged directly to 0.185 in. diam from which cylindrical tensile and compression specimens were machined. Specimen geometry is illustrated in Fig. 1. The gage length was 0.30 in. long and 0.10 in. diam; it should be noted that, apart from the extra heads which are necessary for tensile loading, the geometry and dimensions of the two types of specimen are identical. The specimens were heat treated either by sequence A or B outlined in Table 11. The essential difference between these two treatments is that in one case the material was repeatedly cycled through the y- to a-phase change in order to produce grains of almost random orientation ("random" iron)

Jan 1, 1969

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio&apos;n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews&apos; on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;&apos; will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment &apos; consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Charles S. Barrett

THE experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal&apos;s capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientations resulting from recrystallization and is being extended to other metals and other types of deformation. PREVIOUS WORK The previous experiments are few and have given confusing results. Ono1 compressed a polycrystalline alpha-iron specimen between two flat plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a. double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1938

By Henry S. Rawdon

The structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i,e,, manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the in closures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in " pure " metals in general (etching pits).

Jan 1, 1918

By Harry L. Washburn, Robert L. Llewellyn, W. J. Halvorsen

Many of the problems that occur in the preparation plant originate from practices in the mine. Impurities in raw coal can be in the seam itself or from extraneous material taken in mining from the roof or bottom. In the case of underground mines, the choice of mining equipment will affect the size consist and the amount of extraneous material included with the coal. Also, governmental regulations concerning the degree of rock dusting, gobbing underground, and cleanup have increased the dirt in raw coal. Sulfur dioxide emission standards, on the other hand, are pressuring the coal industry to clean coal more thoroughly. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent (Fig. 1) and only incidentally with mines shipping raw run-of-mine coal crushed to a top size of, usually, 51 to 102 mm (2 to 4 in.), with little, if any, other treatment. JUSTIFICATION FOR COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-range planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and nuclear energy. Coal prices for power plants are still on a Btu (British thermal unit)

Jan 1, 1981

By G. W. Preckshot, N. G. DeLisle, C. E. Cottrell, D. L. Katz

MOST crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank. The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir.

Jan 1, 1942

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.1,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939.3 Two types of process were described: (1) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemi¬spheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. 1);2.4 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ae1, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important 1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenability; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels.* PREVIOUS DATA ON RATE OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan.2 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given.

Jan 1, 1942

By C. Y. Clayton, Francis B. Foley, Muir L. Frey

DuRing the past year, we have investigated the cause of 88 per cent, of the failures by breakage near the bit end of some 1-in. hollow, hexagon, drill steel used in a metal mine. This breakage in the region of the bit end of the steel was peculiarly interesting because we have been Ied to believe that breakage is most prevalent at the shank end of drill steels near the place where the steel is gripped in the chuck of the machine. Records from the mine showed, also, that the breakage was much more frequent in the short lengths of large gage than in the longer steels; this is shown graphically in Fig. 1. Because the shorter lengths of steels are usually those that have been made from broken pieces of long steels or from steels that have worn down in service, rarely being made from new stock, those who are wont to suspect steel of tiring and crystallizing in its old age through fatigue are quite apt to see in this instance an argument in favor of their idea. As usual, a careful examination of these steels reveals defects of a character hardly to be overlooked in favor of such a cause. The steel in question was rolled with a sand core and was of the usual drill steel composition: Carbon 0.85 per cent., manganese 0.60 per cent., silicon 0.25 per cent., phosphorus 0.02 per cent., and sulfur 0.02 per cent., with the exception that in some specimens there was vanadium, not exceeding 0.20 per cent. The following lengths and gages were used: LenGth, GaGe, LenGth. GaGe, Feet Inches feet Inches Starter 2 % 7 111/16 3 2 % 8 11 4 2 % 9 1 9/16 5 2 10 1 7/16 ________6_____________115/16____________________________

Jan 1, 1924